Process for the preparation of lubricating agents for leathers and furs



United States ice 6 Claims. (C1,. 252-857) This invention relates to lubricating or fat-liquoring agents for leather and fur skins and to the method for their preparation.

Water-emulsifiable lubricating agents for leathers and furs are generally prepared by the sulfatization of unsaturated natural and/ or synthetic fats, oils or waxes with conventional sulfatizing agents, e.g. commercial sulfuric acid. As a rule, the sulfatization, which essentially affects double-bonds, is carried on only until a sufficient emulsifiability in water has been attained, so that ordinarily the obtained sulfatization products possess still a considerable number of unsaturated radicals. Due to the ensuing unsaturated character, the oxidation stability (storage life) of the lubricants as well as the light-resistance of the lubricated leathers is unfavorably affected.

It is an object of this invention to obtain lubricating and fat liquoring agents which have a good lubricating effect for leathers and fur skins and have good storage and light stability.

A further object of this invention is to provide a process for obtaining sulfonated fatty materials having an improved storage and light stability.

These and other objects of our invention will become apparent as the description thereof proceeds.

It has now been discovered that it is possible to prepare lubricating agents for leather and furs with satisfactory oxidationand light-stability, when the unsaturated starting materials are first incompletely chlorinated according to known methods, to obtain a partial satura tion of the unsaturated bonds, and then the thus pretreated products are sulfated according to known procedure until a sufficient water emulsifiability has been attained.

According to the degree of chlorination, the unsaturated character of the starting material and with it the characteristics of the sulfated end products can be more or less varied. It has been noted that products with 3 to 15%, preferably 5 to of the chlorine taken up by the unsaturated starting materials (calculated on the starting material), and the degree of the unsaturation of the starting materials measured by the iodine number being reduced 20 to 70%, preferably 30 to 50%, result in lubricating agents with especially favorable characteristics after the usual sulfatization. This advantage is particularly evident in the lightand storage stability of the lubricating agents obtained as well as in the very soft and pliable leathers obtained by treating with these agents.

The starting materials for the process are the following: high-molecular unsaturated hydrocarbons, alcohols, ethers, carboxylic acids, esters and others, e.g. olefins such as dodecenes, octadecenes, squalen, esters of unsaturated high-molecular alcohols with 12 to 20 carbon atoms, in particular of the oleylalcohol or other monoor polyunsaturated alcohols with any lowor high-molecular, monoor polybasic carboxylic acids and ethers of such alcohols. Also suitable are esters of unsaturated high-molecular fatty acids or mixtures thereof such as naturally occurring glycerides, whose fatty acid constituent could be monoor polyunsaturated, such as soybean oil, cottonseed-,

rapeseed-, linseed-, castor-, sunflower-, olive-, neats foot-, herring, codliver-, sharkliver. or whale oil; also unsaturated waxes such as spermoil or their reaction products. Furthermore, as starting materials are suitable: esters of unsaturated fatty acids with monoor polyvalent alcohols of the aliphatic, cycloaliphatic, aromatic or heterocyclic series; also esters of unsaturated carboxylic acids and alcohol mixtures and unsaturated mixed esters of polyvalent alcohols and various unsaturated carboxylic acids. Also usable are esters whose acid as well as alcohol constituent possess a monoor polyolefinic unsaturated hydrocarbon radical. Preferable starting materials are represented in the natural, unsaturated animal and vegetable fats, oils and waxes, because they are suitable and easily available.

The chlorination of the unsaturated starting materials can be accomplished in various ways. The generally known methods of addition of chlorine may be employed e.g. the introduction of gaseous chlorine into the starting material to be chlorinated, where, if necessary, the mixture may be diluted with solvents. It is also possible for example, to add the chlorine to be introduced into the material to be chlorinated in the form of a dispersion in an inert solvent. In any case, by means of adequate cooling care is taken that the heat effect is dissipated to prevent any damage due to secondary reactions.

The sulfatization of the incompletely chlorinated, unsaturated starting materials is done in the conventional manner with 10 to 35%, preferably 12 to 20% of commercial sulfuric acid (98%), based on the material to be sulfonated, at below 40 C., preferably at from 15 to C. As a rule larger quantities of sulfuric acids are needed at a greater reduction of the iodine numbers of the unsaturated starting materials due to the incomplete chlorination at e.g. below and for continuously higher iodine number, e.g. from 50 up, usually smaller amounts of sulfuric acids are needed for adequate sulfatization. Instead of the commercial sulfuric acid, other well known sulfatizating agents may in principle be used, e.g. chlorosulfuric acid, oleum or sulfur trioxide. The washing and neutralizing of the sulfatization products obtained may be accomplished in conventional manner either by washing with saturated or semi-saturated salt solutions and subsequent neutralization, or by a combined washingneutralization process, where the sulfatization product is introduced into a 5% ammonia solution containing circa to of the amount of ammonia necessary for the neutralization. After the separation of the extracted salt water sediment, the neutralization may be finished in the usual manner. It is also possible to undertake the neutralization without separate washing.

In the event that dark-colored sulfatization products result, which happens sometimes with the sulfatization of partially chlorinated herring oils, the sulfatization products may be bleached and deodorized in a weakly acid pH-range, for instance, in combination with the washingneutralizing process at a pH-number of 2.5 to 3 with 5 to 15% (based on the sulfatization product) of 40% hydrogen peroxide at a temperature of circa 50 C. Various other bleaching agents and bleaching methods, possibly at other pH-ranges, may be employed.

By this process, highly lightand storage-stable, oxidation-stable, water-emulsifiable lubricating agents are obtained which in comparison to the sulfatization products not prechlorinated, congeal at low temperature and tend less to salt formation and exudation.

The process according to this invention not only shows advantages with regard to the stability of the lubricants obtained, but also in their application to leathers. The lubricants of the invention show in startling manner, compared to sulfatization products not pre-treated, a

considerably softer and more pliable lubrication effect as well as a fuller leather feel, which can be attained when using conventional lubricating agents, only by means of combinations with other auxiliary means, such as special emulsifiers, neutral fats, etc., wherein these combinations require time-consuming tests.

The described sulfatization products can, as a rule, be used alone, but they may in some cases also be used in combination with neutral oils and synthetic emulsifiers of the anionic, cationic and non-ionic type. By neutral 011s are meant natural and synthetic oils, fats and waxes of plant-, animalor mineral origin, which can also be chlorinated.

The following specific examples are presented to illustrate the invention and to enable persons skilled in the art to better understand and practice the invention and are not intended to be limitative.

Example I A spermwhale oil, filtered and undercooled at 8 C. having the values: acid No. 2.5; saponification No. 135; iodine No. 81, was placed into a flask provided with a cooling coil. Chlorine was slowly introduced with vigorous stirring, the temperature being maintained at 17 C. by cooling. The progress of the reaction was followed by weighing and the chlorination was discontinued when 10.1% of chlorine had been taken up. Then the reaction product was washed with water and diluted sodium bicarbonate solution. The product had the following values: acid No. 1.7; iodine No. 38.2; chlorine content, 10.1%. This intermediate product was then sulfated with 15% of commercial sulfuric acid (98%) at 28 to 30 C. according to known methods, then was stirred for 1 hour. It was subsequently introduced into a solution of 5% ammonia, containing 80% of the ammonia needed for the complete neutralization, at a temperature not above 30 to 40 C. For the purpose of separation of the saltwater layer, the mixture was left standing over night at circa 50 C., then the saltwater layer was decanted and the clean sulfatization product was neutralized with commercial ammonia to an end pH value of 7.0. A clear,

yellow oil was obtained which even after extended storage remained homogeneous and which showed no deposits nor any other changes.

Shoe upper leathers, chrome-tanned, then tanned with synthetic tanning agents or resinous tanning agents, were fat-liquored at a temperature of 60 C. in a drum for 45 minutes by means of a 250% float containing 4.5 to 5.5% of the obtained sulfatization product based on the leather as lubricating substance. The leathers, dried and finished in the conventional manner had a highly soft and pliable feel, and good grain compactness and light-resistance.

Example II A codliver oil, having the values: acid No. 8 to 10; iodine No. 140 to 150; was slowly reacted accompanied by cooling, with a carbon tetrachloride solution containing 10% of chlorine. The tolerance speed was adjusted so that the temperature was kept at C. After absorption of 9.7% of chlorine, the mixture was washed with water and the solvent was distilled off. The reaction product had the following values: acid No. 9.4; iodine No. 99.8; chlorine content, 9.7%. The chlorination product was sulfated with 15% of commercial sulfuric acid according to Example 1. After this, it was introduced into the 5% ammonia solution and then bleached and deodorized with 10% of a 40% hydrogen peroxide by stirring at 50 C. for 10 to 15 minutes. The mixture was left standing over night, during which time the sulfatization product became separated from the saltwater mixture. After decantation from the saltwater layer, this sulfatization product was completely neutralized with commercial ammonia up to a pH 7.0 range. A light, yellow-brown, clear oil was obtained, easily emulsifiable in Water.

Chrome-tanned and dyed leathers for clothes from cow-hides were fat-liquored in a drum for 45 minutes at 60 C. by means of a 250% float with 6 to 8% of lubricating substance consisting of a mixture of 77% of the above sulfatization product, 20% of spermwhale oil and 3% of the reaction product of a mixture of commercial fatty alcohols with chain lengths C C reacted with an 8 mol ethylene oxide.

The leathers, dried and finished according to known methods, Were distinguished by a soft, pliable and full feel as well as by good light-resistance.

Example III A Peruvian fish oil, having the values: acid No. 0.4; saponification No. 196; iodine No. 181; hydroxyl No. 13.4; Was partially chlorinated until attaining the values: acid No. 5.2; iodine No. 130.4; hydroxyl No. 13.4; chlorine content 9.0%. The chlorination product obtained was reacted with 15% of commercial sulfuric acid and submitted to ammonia neutralization in combination with a bleachingand deodorizing process according to Example II.

A light, yellow-brown, clear water emulsifiable oil was obtained.

A combination tanned shoe-upper leather was fatliquored in a drum over a period of 45 minutes by means of a 250% float with 4.5 to 6.0% of lubricating substance of a mixture of 75% of the above sulfatization product and 25% of the partially chlorinated but not sulfatized fish-oil, then dried and finished in the usual manner.

A full, pliable shoe upper leather with good grain formation was obtained.

Example IV Chlorine was added to a fish oil mixture with the values: acid No. 17.5; saponification No. 186.1; iodine No. 125.4, until the values were as follows: acid No. 11.9; iodine No. 82.4; chlorine content 10.1%. According to the procedure of Example II, the chlorination product was sulfatized, bleached and deodorized. A light yellow, clear water emulsifiable oil was obtained.

Pastel colored, chrome-tanned glove leather of lambs skins was fat-liquored in a drum for 45 minutes at 60 C. by means of a 250% float with 4 to 6% of lubricating substance, consisting of a mixture of 60% of the above sulfatization product, 20% of the partially chlorinated, but not sulfatized fish oil, 15 of paraflin oil of a viscosity having a viscosity index of 5 E. (Engler) at a temperature of 20 C., 5% of the product of a mixture of commercial fatty alcohols with a chain length of C C reacted with 8 mol ethylene oxide. The treated leather was dried and finished in conventional manner. Especially soft and pliable as well as stretchable glove leathers of good light-resistance were obtained.

Example V A teaseed oil with a starting iodine number of to was partially chlorinated until the iodine number reached 45, then sulfatized with 18% of commercial sulfuric acid, according to the procedure of Example 1. Sub sequent to the neutralization, a clear, yellow-brown, water-emulsifiable oil was obtained.

Shoe upper leathers, first chrome-tanned, then tanned with synthetic or resinous tanning agents were fat-liquo-red in a drum for a period of 45 minutes at 60 C. by means of a 250% float with 4.5 to 5.5% lubricating substance of a mixture of 70% of the above sultfatization product and 30% of the partially chlorinated, but not sulfatized teaseed oil, then dried and finished. The leathers obtained for shoe uppers were distinguished by a full, soft and pliable feel as well as good light-resistance.

Example VI A commercial triolein with an iodine No. of 85 to 90 was partially chlorinated until it had an iodine No. of

about 50, according to the procedure of Example I, then sulfatized and neutralized.

Pastel-colored and white leathers for clothes were fatliquored in a drum at 60 C. over a period of 45 minutes by means of a 250% float with a 6 to 8% of lubricating substance of a mixture of 70% of the above sulfatization product, 26% of the partially chlorinated, :but not sulfated triolein and 4% of an acid monoethanola-mide of coconut oil reacted with a 4 mol ethyleneoxide, then dried and finished.

The clothing leathers obtained distinguished themselves by good light-resistance and by a soft, pliable and full feel.

While certain specific examples and preferred modes of practice of the invention have been set forth it will be understood that this is solely for the purpose of illustration and that various changes and modifications may be made without departing from the spirit of the disclosure and the scope of the appended claims.

We claim:

1. A process for the preparation of water emulsifiable lubricating agents for leathers and furs which comprises the steps of partially chlorinating an unsaturated material selected from the group consisting of olefins of 12 to 30 carbon atoms and higher [fatty materials selected from the group consisting of naturally occurring unsaturated fats, oils and waxes with chlorine, whereby the iodine number of said unsaturated material is reduced by from 20% to 70%, and the partially chlorinated unsaturated material contains from about 3% to about 15% of 30 chlorine, based on the starting material, sulfatizing the resulting partially chlorinated unsaturated material by the action, of 10% to based on the material to be sulfatized, of a sulfatizing agent selected from the group consisting of sulfuric acid, chlorosulfuric acid, oleum and sulfur trioxide at a temperature below about C., neutralizing the sulfatized material with ammonia and recovering said water emulsifiable lubricating agent.

2. The process of claim 1 wherein said partially chlorinated unsaturated material contains from 5% to 10% of chlorine and the iodine number is reduced from 30% to based on the starting material.

3. The process of claim 1 wherein said unsaturated material is a naturally occurring oil.

4. The process of claim 1 wherein said sul fatizing agent is commercial sulfuric acid.

5. The process of claim 4 wherein 12% to 20%, based on the material to be sulfatized, of commercial sulfuric acid is employed.

6. The water emulsifiable lubricating agents for leathers and furs produced by the process of claim 1.

References Cited UNITED STATES PATENTS 1,957,324 5/1934 Dam'bacher 252-8.57 2,630,408 3/1953 Lighthipe et al 2528.57 2,974,000 3/1961 Retzch et al 2528.57

LEON D. ROSDOL, Primary Examiner.

I. T. FEDIGAN, Assistant Examiner. 

1. A PROCESS FOR THE PREPARATION OF WATER EMULSIFIABLE LUBRICATING AGENTS FOR LEATHERS AND FURS WHICH COMPRISES THE STEPS OF PARTIALLY CHLORINATING AN UNSATURATED MATERIAL SELECTED FROM THE GROUPCONSISTING OF OLEFINS OF 12 TO 30 CARBON ATOMS AND HIGHER FATTY MATERIALS SELECTED FROM THE GROUP CONSISTING OF NATURALLY OCCURRING UNSATURATED FATS, OILS AND WAXES WITH CHLORINE, WHEREBY THE IODINE NUMBER OF SAID UNSATURATED MATERIAL IS REDUCED BY FROM 20% TO 70%, AND THE PARTIALLY CHLORINATED UNSATURATED MATERIAL CONTAINS FROM ABOUT 3% TO ABOUT 15% OF CHLORINE, BASED ON THE STARTING MATERIAL, SULFATIZING THE RESULTING PARTIALLY CHLORINATED UNSATURATED MATERIAL BY THE ACTION, OF 10% TO 35%, BASED ON THE MATERIAL TO BE SULFATIZED, OF A SULFATIZING AGENT SELECTED FROM THE GROUP CONSISTING OF SULFURIC ACID, CHLOROSULFURIC ACID, OLEUM AND SULFUR TRIOXIDE AT A TEMERATURE BELOW ABOUT 40*C., NEUTRALIZING THE SULFATIZED MATERIAL WITH AMMONIA AND RECOVERING SAID WATER EMULSIFIABLE LUBRICATING AGENT. 